WO1996012579A1 - Melanges de fonderie et leurs emplois - Google Patents

Melanges de fonderie et leurs emplois Download PDF

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Publication number
WO1996012579A1
WO1996012579A1 PCT/US1995/012822 US9512822W WO9612579A1 WO 1996012579 A1 WO1996012579 A1 WO 1996012579A1 US 9512822 W US9512822 W US 9512822W WO 9612579 A1 WO9612579 A1 WO 9612579A1
Authority
WO
WIPO (PCT)
Prior art keywords
foundry
acetoacetate
ethylenically unsaturated
acetoacetate ester
ester
Prior art date
Application number
PCT/US1995/012822
Other languages
English (en)
Inventor
Paul Shau Lung Chan
Satish S. Jhaveri
W. Graham Carpenter
Original Assignee
Ashland Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Inc. filed Critical Ashland Inc.
Priority to AU37632/95A priority Critical patent/AU3763295A/en
Publication of WO1996012579A1 publication Critical patent/WO1996012579A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2266—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

Definitions

  • the foundry mixes comprise (a) a foundry aggregate, and (b) a foundry binder comprising in admixture: (1) an acetoacetate ester; (2) an ⁇ , ⁇ ethylenically unsaturated monomer, preferably an acrylate; and (3) a liquid tertiary amine catalyst having a pK value of 12-14.
  • the foundry mixes are used to prepare foundry shapes made from foundry mixes by a no- bake process.
  • sand casting In the foundry industry, one of the processes used for making metal parts is sand casting.
  • sand casting disposable foundry shapes (usually characterized as molds and cores) are made by shaping and curing a foundry mix which is a mixture of sand and an organic or inorganic binder. The binder is used to strengthen the molds and cores.
  • One of the processes used in sand casting for making molds and cores is the no-bake process. In this process, a foundry aggregate, binder, and liquid curing catalyst are mixed and compacted to produce a cured mold or core. In the no-bake process, it is important to formulate a foundry mix which will provide sufficient worktime to allow shaping. Worktime is the time between when mixing begins and when the mixture can no longer be effectively shaped to fill a mold or core.
  • a binder commonly used in the no-bake process is a polyurethane binder derived by curing a polyurethane-forming binder with a liquid tertiary amine catalyst.
  • Such polyurethane-forming binders used in the no-bake process have proven satisfactory for casting such metals as iron or steel which are normally cast at temperatures exceeding about 1400°C. They are also useful in the casting of light-weight metals, such as aluminum, which have melting points of less than 700°C.
  • the polyurethane-forming binder usually consists of a phenolic resin component and polyisocyanate component which are mixed with sand prior to compacting and curing.
  • the phenolic resin component generally contain small amounts of free phenol, free formaldehyde and organic solvent, all of which can be obnoxious to smell and can create stress for the environment. Because of this, there is an interest in developing foundry binders which do not contain free phenol, free formaldehyde, and organic solvents.
  • the foundry mixes can be used to prepare foundry shapes such as molds and cores by a no-bake process.
  • the binder system is free of formaldehyde, phenol, and organic solvents. Work and strip time, which are dependent on the sand used, can be varied by changes in the catalyst level used.
  • the invention also relates to a process for preparing such foundry shapes and metal castings prepared with such shapes. DETAILED DESCRIPTION AND BEST MODE
  • Acetoacetate esters can be prepared according to well known methods by the transesterification of a polyhydroxyl compound with an alkyl, preferably ethyl or t-butyl, acetoacetate to liberate an alkyl alcohol and form the ester.
  • the polyhydroxyl compound, or blends thereof typically have an average functionality of at least 2.
  • the polyhydroxyl compound and acetoacetate ester are reacted in the presence of triphenylphosphite catalyst at a temperature of 120°C to 150°C for 2.5 to 10 hours such that the molar ratio of polyhydroxyl compound to acetoacetate ester is such that there is about one molar equivalent of acetoacetate ester for each molar equivalent of hydroxyl groups.
  • the polyhydroxy functional group may be derived from any hydroxyl containing compound, for instance 1,3-butane diol, 1,4-butane diol, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, diethylene glycol, dimethylol propionic acid, dipropylene glycol, ethylene glycol, 1,6-hexanediol, hexylene glycol, neopentyl glycol, 1,5-pentanediol, propylene glycol, tetraethylene glycol, triethylene glycol, trimethylene glycol, trimethylpentanediol, glycerine, trimethylol ethane, trimethylol propane, pentaerythritol, and combinations of two or more of these.
  • Preferably used as the polyhydroxyl compound are hydroxyl compounds with an average functionality of 2 to 4 such as glycerine, trimethylol ethane, trimethylol propane, pentaery
  • Typical acetoacetates which can be used to prepare the multifunctional acetoacetate esters include methyl acetoacetate, ethyl acetoacetate, and the like. Preferably used is tert-butyl and ethyl acetoacetate.
  • acetoacetate esters include cyclohexanedimethanol bis-acetoacetate, glycerol triacetoacetate, neopentyl glycol bis-acetoacetate, ethylene glycol bisacetoacetate, trimethylolpropane tris- acetoacetate, pentaerythritol tetrakis-acetoacetate, acetoacetylated polyvinyl alcohols, acetoacetylated polyester resins, and mixtures thereof, preferably glycerol triacetoacetate, trimethylolpropane tris-acetoacetate, pentaerythritol tetrakis-acetoacetate.
  • Preferred ⁇ , ⁇ ethylenically unsaturated monomers are ethylenically unsaturated monomers such as pentaerythritol triacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, and tetraethylene glycol diacrylate.
  • the preferred equivalent ratio of acetoacetate ester to ⁇ , ⁇ ethylenically unsaturated monomer is from 0.8:1 to 1.2:1.0.
  • One equivalent is defined as the molecular weight divided by the number of reactive functional groups.
  • subject foundry binders are reactive because the alpha, gamma carbonyls of the acetoacetate ester activates the hydrogen on the methylene group of the acetoacetate ester to form a carbanion which is capable of adding across a polarized double bond of an , ⁇ ethylenically unsaturated compound in a Michael addition.
  • This addition to the multifunctional ⁇ , ⁇ ethylenically unsaturated compound produces a cure or crosslinking reaction in the presence of a strong base. Since the reaction occurs only in the presence of strong base, the acetoacetate ester and ⁇ , ⁇ ethylenically unsaturated monomer can be blended and are stable until exposed to the strong base.
  • the strong basic catalyst (Part I) is preferably applied to the sand first, and the blend of the acetoacetate ester and ⁇ , ⁇ ethylenically unsaturated monomer (Part II) are then applied to the sand.
  • Optional ingredients for the binder include release agents and adhesion promoters, such as silanes described in U.S. Patent 4,540,724 which is hereby incorporated into this disclosure by reference, to improve humidity resistance.
  • the strong base is a liquid amine catalyst having a pK b value generally in the range of from 12 to 14.
  • Suitable catalysts which may be used include 1, 8-diaza-bicyclo (5.4.0) undecene-7 (POLYCAT DBU) , tetramethyl guanidine, 1,4- dihydropyridine, and 2-allyl-N-alkylimidazoline.
  • the term "liquid amine” is meant to include amines which are liquid at ambient temperature or those in solid form which are dissolved in appropriate solvents.
  • the pK value is the negative logarithm of the dissociation constant of the base and is a well-known measure of the basicity of a basic material. The higher this number is, the weaker the base.
  • the bases falling within this range are generally organic compounds containing one or more nitrogen atoms.
  • Preferred bases are heterocyclic compounds containing at least one nitrogen atom in the ring structure.
  • catalyst concentrations will vary widely. In general, the lower the pK b value is, the shorter will be the worktime of the composition and the faster, more complete will be the cure. Solvents and any acidity present in added ingredients such as sand may affect the catalytic activity. In general, however, catalyst concentrations will be a catalytically effective amount which generally will range from about 0.5 to about 25.0 percent by weight of the blend of acetoacetate ester and ⁇ , ⁇ ethylenically unsaturated monomer, preferably 5.0 percent by weight to 15.0 percent by weight, most preferably 5.0 percent by weight to 15 percent by weight based upon the weight of the acetoacetate ester.
  • the catalyst level is adjusted to provide a worktime for the foundry mix of 3 minutes to 10 minutes, preferably 8 minutes to about 10 minutes, and a striptime of about 4 minutes to 12 minutes, preferably 9 minutes to about 10 minutes.
  • Worktime is defined as the time interval after mixing the acetoacetate ester, ⁇ , ⁇ ethylenically unsaturated monomers, and catalyst with the sand and the time when the foundry shape reaches a level of 60 on the Green Hardness "B" Scale Gauge sold by Harry W. Dietert Co., Detroit, Michigan.
  • Striptime is time interval after mixing the acetoacetate ester, ⁇ , ⁇ ethylenically unsaturated monomer, and catalyst and the time when the foundry shape reaches a level of 90 on the Green Hardness "B” Scale Gauge.
  • foundry mixes Various types of aggregate and amounts of binder are used to prepare foundry mixes by methods well known in the art. Ordinary shapes, shapes for precision casting, and refractory shapes can be prepared by using the binder systems and proper aggregate. The amount of binder and the type of aggregate used is known to those skilled in the art.
  • the preferred aggregate employed for preparing foundry mixes is sand wherein at about 70 weight percent, and preferably at least about 85 weight percent, of the sand is silica.
  • suitable aggregate materials for ordinary foundry shapes include zircon, olivine, aluminosilicate, chromite sand, and the like.
  • the amount of aggregate used in the foundry mix is a major amount, generally at least 70 weight percent based on the weight of the foundry mix, more typically 80 weight percent, preferably 85 weight percent, and most preferably from 90 weight percent to 98 weight percent.
  • the amount of binder is generally no greater than about 15% by weight and frequently within the range of about 0.5% to about 10% by weight based upon the weight of the aggregate.
  • the binder content for ordinary sand foundry shapes ranges from about 0.6% to about 5% by weight based upon the weight of the aggregate in ordinary sand-type foundry shapes.
  • test specimens were produced by the no-bake process using 1, 8-diaza-bicyclo (5.4.0) undecene-7 (POLYCAT DBU) as a 50 percent solution in HI-SOL 10. All parts are by weight and all temperatures are in °C unless otherwise specified.
  • the foundry mixes were prepared by first mixing the catalyst with the sand for about for 2 minutes. Then the blend of acetoacetate ester and ⁇ , ⁇ ethylenically unsaturated monomer were added to the sand and mixed for an additional 2 minutes.
  • Measuring the tensile strength of the dog bone shapes enables one to predict how the mixture of sand and binder will work in actual foundry operations.
  • Lower tensile strengths for the shapes indicate that the binder reacted more extensively during mixing with the sand prior to forming foundry shapes, and thus were not suitable for forming foundry shapes.
  • the foundry shapes were stored 1 hour, 3 hours and 24 hours in a constant temperature room at a relative humidity of 50% and a temperature of 25°C before measuring their tensile strengths. Unless otherwise specified, the tensile strengths were also measured on shapes stored 24 hours at a relative humidity (RH) of 100%.
  • AAE acetoacetate ester AAEP acetaoacetate ester of t-butylacetoacetate and pentaerythritol.
  • BOB based on binder.
  • BOS based on sand.
  • Sartomer 349 is the diacrylate of ethoxylated Bisphenol
  • TMPTA trimethyol propane triacrylate.
  • AAE tetraacetoacetate ester .of pentaerythritol
  • the AAEP was blended with a mixture of TMPTA and Sartomer 349, another ⁇ , ⁇ ethylenically unsaturated monomer which is the diacrylate of ethoxylated Bisphenol A.
  • This blend is called ECOLYN and has a mole ratio of AAEP/TMPTA/Sartomer of 1.0/0.5/1.2.
  • the AAEP/TMPTA/Sartomer blend was sand tested on Canadian Lake (construction aggregate American sand), U.S. Wedron 5010, Wedron 540, and Manley 1L5W using POLYCAT DBU 15% BOB.
  • the catalyst (Part I) was mixed with the sand, and then the blend (Part II) was added. Results of testing with various types of sand. Examples 1-6, are shown in Table I.
  • the ECOLYN blend was tested at various mole ratios of AAEP, TMPTA, and Sartomer 349 with and without the Sartomer 349.
  • Sand tests were conducted on Canada Lake and Wedron 5010 sand and are summarized in Table II. The best results were obtained using a mole ratio of AAEP/TMPTA/Sartomer 349 of 1.0/1.3/0, i.e. without the Sartomer 349.
  • Core wash resistance was evaluated on a binder made with a Part II consisting of a 1.0/1.3 mole ratio of AAEP/TMPTA. Tensile strengths of the cores were good in normal sand tests. After dipping in CERAMCOTE ZWK-20-A core wash, test specimens were dried for 15 minutes at about 180°C and tested hot and after cooling for one hour. Hot tensiles were poor, but the cooled test specimens had very high strength. See Example 16 of Table IV.
  • Iron castings were improved when Ceramcote ZWK-20A was used as a core wash for cores made with the binders. Castings improved when both air dried and oven dried cores were tested for erosion, veining, and penetration, although erosion was excellent for air dried cores, but very poor for oven dried cores. Penetration castings on Manley 1L5W sand compared favorably with cores prepared with commercially available binders.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention porte sur des mélanges de fonderie et leur utilisation. Lesdits mélanges comprennent: (a) un agrégat de fonderie et (b) un liant de fonderie et comme adjuvants: (1) un acétoacétate ester, (2) un monomère portant une insaturation éthylénique en α-β, et (3) un catalyseur liquide d'amine tertiaire présentant un pK de 12 à 14. Lesdits mélanges de fonderie servent à préparer des moules par un procédé sans cuisson
PCT/US1995/012822 1994-10-21 1995-10-13 Melanges de fonderie et leurs emplois WO1996012579A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37632/95A AU3763295A (en) 1994-10-21 1995-10-13 Foundry mixes and their uses

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/327,465 1994-10-21
US08/327,465 US5459178A (en) 1994-10-21 1994-10-21 Foundry mixes and their uses

Publications (1)

Publication Number Publication Date
WO1996012579A1 true WO1996012579A1 (fr) 1996-05-02

Family

ID=23276658

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/012822 WO1996012579A1 (fr) 1994-10-21 1995-10-13 Melanges de fonderie et leurs emplois

Country Status (3)

Country Link
US (1) US5459178A (fr)
AU (1) AU3763295A (fr)
WO (1) WO1996012579A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009017064A1 (fr) * 2007-08-01 2009-02-05 Adeka Corporation Composition de résine photosensible développable par des alcalis et composé de β-dicétone
JP2009037003A (ja) * 2007-08-01 2009-02-19 Adeka Corp アルカリ現像性感光性樹脂組成物
JP2009209105A (ja) * 2008-03-05 2009-09-17 Adeka Corp カルバゾリル基を有するβ−ジケトン化合物及び該化合物を用いた光重合開始剤
JP2009244447A (ja) * 2008-03-31 2009-10-22 Adeka Corp アルカリ現像性感光性樹脂組成物

Families Citing this family (19)

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EP0944664B1 (fr) * 1996-12-11 2002-03-20 Minnesota Mining And Manufacturing Company Resine susceptible de durcir a temperature ambiante
US6204343B1 (en) 1996-12-11 2001-03-20 3M Innovative Properties Company Room temperature curable resin
US5913970A (en) * 1997-01-16 1999-06-22 Eastman Chemical Company Stabilized non-polymeric acetoacetate esters that promote adhesion to metallic and oxidized substrates
US6326418B1 (en) * 1997-09-12 2001-12-04 Kao Corporation Acid-curable, refractory particulate material composition for forming mold
US6025410A (en) * 1997-09-19 2000-02-15 Ashland Inc. Liquid oligomers containing acrylate unsaturation
US5945489A (en) * 1997-09-19 1999-08-31 Ashland, Inc. Liquid oligomers containing unsaturation
WO2000068331A1 (fr) * 1999-05-05 2000-11-16 E.I. Du Pont De Nemours And Company Compositions de revetement contenant des macromolecules de haute structure
US6342543B1 (en) 1999-09-24 2002-01-29 Ashland Inc. Amine curable foundry binder system
AU4885002A (en) 2001-07-03 2003-01-09 Rohm And Haas Company Composition method of making and method of using adhesive composition
US8013068B2 (en) * 2003-01-02 2011-09-06 Rohm And Haas Company Michael addition compositions
US7332546B2 (en) * 2004-10-01 2008-02-19 3M Innovative Properties Company Ring-opened azlactone telechelic polymer
US7304112B2 (en) * 2004-10-01 2007-12-04 3M Innovative Properties Company Azlactone telechelic polymer
US7307106B2 (en) * 2004-12-10 2007-12-11 3M Innovative Properties Company Photocurable Michael addition polymers
US8609131B2 (en) * 2005-01-25 2013-12-17 3M Innovative Properties Company Absorbent dressing comprising hydrophilic polymer prepared via Michael reaction
US7335690B2 (en) * 2005-01-25 2008-02-26 3M Innovative Properties Company Crosslinkable hydrophilic materials from polymers having pendent Michael donor groups
US20220056171A1 (en) 2018-12-18 2022-02-24 Arxada Ag Isocyanate Free Binder
US11802104B2 (en) 2019-04-03 2023-10-31 Arxada Ag Method for preparation of acetoacetylated polyols
CN110105799B (zh) 2019-05-07 2021-10-01 广东华润涂料有限公司 木器用涂料组合物以及由其制成的木制品
WO2021009366A1 (fr) 2019-07-17 2021-01-21 Lonza Solutions Ag Procédé de préparation d'éthylène glycol acétoacétylé décoloré

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US4366269A (en) * 1979-06-09 1982-12-28 Nissan Motor Co., Ltd. Resin coated foundry sand using crystalline unsaturated polyester as binder
US4568728A (en) * 1984-07-16 1986-02-04 Delta Resins & Refractories Foundry binder with improved breakdown and improved thermal reclamation properties
US5017649A (en) * 1988-01-19 1991-05-21 Eastman Kodak Company Low temperature Michael addition reactions
US5288804A (en) * 1992-01-03 1994-02-22 Reichhold Chemicals, Inc. Acetoacetate aromatic aldimine resin composition
US5321118A (en) * 1993-09-30 1994-06-14 Eastman Chemical Company 1-acetoacetamido-2,3-propane diol monomer and polyesters prerpared therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4366269A (en) * 1979-06-09 1982-12-28 Nissan Motor Co., Ltd. Resin coated foundry sand using crystalline unsaturated polyester as binder
US4568728A (en) * 1984-07-16 1986-02-04 Delta Resins & Refractories Foundry binder with improved breakdown and improved thermal reclamation properties
US5017649A (en) * 1988-01-19 1991-05-21 Eastman Kodak Company Low temperature Michael addition reactions
US5288804A (en) * 1992-01-03 1994-02-22 Reichhold Chemicals, Inc. Acetoacetate aromatic aldimine resin composition
US5321118A (en) * 1993-09-30 1994-06-14 Eastman Chemical Company 1-acetoacetamido-2,3-propane diol monomer and polyesters prerpared therefrom

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009017064A1 (fr) * 2007-08-01 2009-02-05 Adeka Corporation Composition de résine photosensible développable par des alcalis et composé de β-dicétone
JP2009037003A (ja) * 2007-08-01 2009-02-19 Adeka Corp アルカリ現像性感光性樹脂組成物
US8338081B2 (en) 2007-08-01 2012-12-25 Adeka Corporation Alkali-developable photosensitive resin composition and β-diketone compound
JP2009209105A (ja) * 2008-03-05 2009-09-17 Adeka Corp カルバゾリル基を有するβ−ジケトン化合物及び該化合物を用いた光重合開始剤
JP2009244447A (ja) * 2008-03-31 2009-10-22 Adeka Corp アルカリ現像性感光性樹脂組成物

Also Published As

Publication number Publication date
AU3763295A (en) 1996-05-15
US5459178A (en) 1995-10-17

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